Organopolysiloxanes



United States Patent 3,355,425 ORGANOPOLYSILOXANES Loren A. Haluska,Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich., acorporationrof Michigan No Drawing. Original application Aug. 6, 1964,Ser. No. 387,988. Divided and this application Jan. 16, 1967, Ser. No;619,109 A r Claims. (Cl. 26046.5)

ABSTRACT OF THE DISCLOSURE 'A thermoplastic, elastomeric and resinoussiloxane polymer of at least one unit of the formula This is a divisionof application-Sen No. 387,988, filed Aug. 6, 196 1 a This applicationrelates to novel organosilicon compounds that are useful as sizingagents, 'elastomeric ma- 1 5; ke..-

The compounds of this invention includebot-h silanes and siloxanes. Anysilanerof this invention can be described as being a compound of theformula 0 (B) ncmcmsm',

where Q is a lower alkyl radical, R is a divalent radical free ofaliphatic unsaturation selected from the group consisting of hydrocarbonradicals and radicals containing carbon, hydrogen, and oxygen ,in anether linkage, R is selected from the group consisting of monovalenthydrocarbon radicals free of aliphatic unsaturation, thehydrox'ylzgroupj and hydrolyzablegroups,-n is an integer of 0 to 1, andmis an integer of 0 to 2.

Q can be any lowervalkyl'radical such a methyl, ethyl,isopropyLn-pentyl, or isohexyl.

;R can be any divalentra'dical, as defined above, such as methylene,ethylene, propylene, decylene, octadecylene, 2,5'-octy1ene,

Patented N 0v, 28', 1967 'ice R' can be any monovalent hydrocarbonradical free of aliphatic unsaturation; e.g. alkyl groups such asmethyl, ethyl, isopropyl, n-hexyl, Z-ethylhexyl and octadecyl;cycloaliphatic groups such as cyclohexyl and cyclopentenyl; andaromatic-containing groups such as phenyl, tolyl, benzyl,fl-phenylpropyl, xenyl' and naphthyl, R can also be the hydroxyl groupor any hydrolyzable groups known to the art; e.g., lower alkoxy groupssuch as methoxy, ethoxy, isopropoxy, butoxy or isohexoxy; alkoxyalkylgroups such as fi-methoxyethoxy, fl-ethoxyethoxy, and

O (CH CH O) CH acyloxy groups such as formate, acetate, propionate orbutyrate; hydrocarbyl-substituted isocyanoxy groupssuch as halogengroups: F, Cl, Br, or I; or the'isocyanate group. The siloxanes of thisinvention are polymeric compositionscontaining at least one unit of theformula: Qm 0(R iomcrns i0 where Q is a lower alkyl radical, R is adivalent radical, free of aliphatic unsaturation, selected from thegroup consisting of hydrocarbon radicalsand radicals containing carbon,hydrogen, and oxygen in an ether linkage, R

is selected from the group consisting of monovalent hydrocarbon radicalsfree of aliphatic unsaturation, the hydroxyl group, and hydrolyzablegroups, n is an integer of 0 to'l, and m' and a'are integers of 0 to 2,any other units present being of the formula ZbSiO r where Z is selectedfrom the group consisting of monovalent hydrocarbon and halohydrocarbonradicals," and bisanintegerof0to3. P

Examples of Q, R, and R are given above.

Z can be any monovalent hydrocarbon radical; e.g., alkyl radicals suchas rnethyl, ethyl, isopropyl, n-hexyl, Z-ethylhexyl,andoctadecyl;unsaturated radicals-such as vinyl, ethynyl, allyl, butadienyl, orr 5hexenyl cycloali-' 'phatic radicalssuch as cyclohexyl -or cyclopentenyl;and aromatic containing radicals such as phenyl, tolyl, benzyl,fi-phenylpropyl, xenyl or naphthyl. Z can also be any monovalenthalohydrocarbon radicalieg; haloalkyl such as chloromethyl,3,3,3-trifluoropropyl, fl-(perfluoroheptyl)ethyl, or 4-bromohexyl;unsaturated radicalssuch as 3-chloroallyl or 4,4-difluorobutadienyl;cyclohaloaliphatic radicals such as cholorocyclohexyl o'riodocyclopentenyl; and aromatic-containing radicals such asfluorophenyl, a,a,a-trifluorotolyl, or chlorobenzyl.

with HSiR in the presence of a platinum catalyst such as chloroplatinicacid and a suitable solvent such as xylene. If desired, a vinylpolymerization inhibitor such as hydroquinone can also be added;

. The reaction is:

O (R) C HzCHzSiR's When n is zero, a -CH CH group connects thepyridyloxy group to the silicon atom, i.e.

Q... om

OCH=CH HSiR'a @OCHaCHzSiB/a N N Elevated temperature accelerates thereaction, but temperature, pressure, and proportion of reactants all arenot critical. It is, however, desirable to use such pressure that thereaction temperature is below the boiling point of the reactants.

The siloxanes of this invention can be made by hydrolyzing andcondensing silanes of this invention which contain hydrolyzable Rgroups. This hydrolysis reaction is well-known to the art- A pure formof silane can be hydrolyzed to form siloxane'"hom0p.olymeIS, or mixturesof silanes can be hydro lyzed to form siloxane copolymers. More than onespecies of silane of this invention can be cohydrolyzed, if desired,as'can also other known silanes of the formula Z SiR where Z and b aredefined above, and R is a hydrolyzable group, as defined above.

The siloxanes of this invention can also be made by reacting i .0 (R)non -c111 s N with a siloxane which contains silicon-bonded hydrogen inthe presence of a platinum catalyst. This type of reaction isillustrated in the examples below.

The silanes of this invention are suitable as sizing agents andsurfactants, while the siloxanes of this invention are useful therm pltic, elast meric, and resinousmaterials- The following examples areillustrative only and h uld not be construed as limiting the invention,which is prop erly delineated inthe appended claims.

Example 1 A composition consisting of 270.3 g. of .2-a11y1oxypyridine,268. g. ofmethyldiethoxysilane, 248.6 of xyle and 2.0 g. of a solutionof chloroplatinic acid in .dimethylph ha1ate-(1% by weight platinum) wasrefluxed at 130 to 143.5 C. for 27 hours.

On distillation there was recovered 198.9 g. of

oonioHion s uoczfim 4 which has a boiling point of 165 C. at 20 mm. Hgpressure, a viscosity at 25 of 332cc. an 11:1 9i l.-.4.. V

A portion of this product was placed in a container with a large excessof distilled water and a small amount of KOH. On heating at C. for about12 hours, a viscous oil was formed which was a homopolymer comprising(ll-H: o onicmoms io j units. 2

Example 2 One mol (222 g.) of bis-[flime hylsiloxflmethylsilane washeated to 96 C. with 1 g. of isopropanol (1% Pt).

2-allyloxypyridine was added dropwise, the temperature being allowed torise to 123* (3., until one mole 135.5 3.) had been added. 4

The mixture was then refluxed at 140. 'C. for 12 hours. A sizable yieldof chloroplatinic acid in was recovered.

Example 3 To 294.7 g. of phenyldimethylsilane, 2.3 g. of chloro platinicacid in isopropyl alcohol 1% Pt), and 318 g. of xylene, there wasadded-about 279 g. of 2-allyloxypyridine.

The mixture was refluxed for 42 150 C.

On distillation, 118 g. of

hours from 120 is were recovered, as determined by nuclear magnetic res'chance andinfra-red spectra. 7

Example 4 When 0.2 mole of QG1H14CH-CH:

v.N i ea ed wi h 0.1 mole of "CH3 (E ia/ n (3H3 in the'prese'nce ofplatinum, a compound of the formula 15 produced.

Example 5 When 0.1 mole of CH /--C':H5"

is heated with 0.1 mole of usuooug,

in the presence of platinum, a compound of the formula NOO @omomsuocnm IO1 02H:

is formed.

That which is claimed is:

1. A polymeric composition containing at least one unit of the formulaGOCRhCHzCHzSIiOE N R. 2

where Q is a lower alkyl radical, R is a divalent radical, free ofaliphatic unsaturation, selected from the group consisting ofhydrocarbon radicals and radicals containing carbon, hydrogen, andoxygen in an ether linkage, R is selected from the group consisting ofmonovalent hydrocarbon radicals free of aliphatic unsaturation, thehydroxyl group, and hydrolyzable groups, n is an integer of 0 to 1, andm and a are integers of 0 to 2, any other units present being of theformula where Z is selected from the group consisting of monovalenthydrocarbon and halohydrocarbon radicals, and b is an integer of 0 to 3.

2. The composition of claim 1 where R is methylene.

3. The composition of claim 1 where R and Z are both methyl radicals.

4. A homopolymer comprising units.

2 O CHzCH2CHzSi[OSi(CH References Cited UNITED STATES PATENTS 3,071,5611/1963 Bluestein 26046.5

DONALD E. CZAIA, Primary Examiner.

M. MARQUIS, Assistant Examiner.

1. A POLYMERIC COMPOSITION CONTAINING AT LEAST ONE UNIT OF THE FORMULA